Epoxy based reinforcing patches having improved damping loss factor

Abstract

A reinforcing sheet including one or more layers of a reinforcing material, and a thermosetting adhesive associated with the reinforcing material, wherein the thermosetting adhesive includes a curing agent, and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network.

Claims

1. A reinforcing sheet, comprising: at least one layer of a reinforcing material; and a thermosetting adhesive associated with at least a portion of the reinforcing material, wherein the thermosetting adhesive includes a curing agent, and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network, wherein the curing agent comprises at least one of a boron trifluoride-amine complex, an organic-acid hydrazide, and dicyandiamide.

2. The reinforcing sheet according to claim 1, wherein the reinforcing material comprises a woven fabric.

3. The reinforcing sheet according to claim 2, wherein the reinforcing material comprises woven fiberglass.

4. The reinforcing sheet according to claim 3, wherein the woven fiberglass ranges in thickness from 0.25 mm to 5.00 mm.

5. The reinforcing sheet according to claim 4, wherein the woven fiberglass ranges in thickness from 0.75 mm to 2.50 mm.

6. The reinforcing sheet according to claim 4, wherein the thermosetting adhesive further comprises at least one of microspheres, and a blowing agent.

7. The reinforcing sheet according to claim 1, wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00015## wherein R.sub.1 is selected from the group consisting of an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and cyano group containing 1 to 40 carbon atoms.

8. The reinforcing sheet according to claim 1, wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00016## wherein R.sub.1 is selected from the group consisting of an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and cyano group containing 35 to 40 carbon atoms.

9. The reinforcing sheet according to claim 1, wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00017## wherein R.sub.1 is tall oil based.

10. The reinforcing sheet according to claim 1, wherein the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2 wherein A.sub.1 is represented by the following chemical structure: ##STR00018## wherein R.sub.1 is selected from the group consisting of an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and cyano group containing 1 to 75 carbon atoms, an oligomer, and/or a polymer; and wherein A.sub.2=A.sub.1 and/or comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and cyano group containing 1 to 35 carbon atoms, an oligomer, and/or a polymer.

11. The reinforcing sheet according to claim 1, wherein the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2 wherein A.sub.1 is represented by the following chemical structure: ##STR00019## wherein R.sub.1 is selected from the group consisting of an alkyl, alkenyl, and alkynyl group containing 1 to 36 carbon atoms, an oligomer, and/or a urethane polymer; and wherein A.sub.2=A.sub.1.

12. A reinforcing sheet, comprising: at least one layer of a reinforcing material, wherein the reinforcing material comprises woven fiberglass, and wherein the woven fiberglass ranges in thickness from 0.75 mm to 2.50 mm; a thermosetting adhesive associated with at least a portion of the reinforcing material, wherein the thermosetting adhesive includes a curing agent, and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network; wherein the curing agent is represented by at least one of the following tautomeric chemical structures: ##STR00020## wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00021## wherein R.sub.1 is selected from the group consisting of an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and cyano group containing 35 to 40 carbon atoms; and wherein the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2 wherein A.sub.1 is represented by the following chemical structure: ##STR00022## wherein R.sub.1 is selected from the group consisting of an alkyl, alkenyl, and/or alkynyl group containing 1 to 36 carbon atoms, an oligomer, and a urethane polymer; and wherein A.sub.2=A.sub.1.

13. The reinforcing sheet according to claim 12, wherein the thermosetting adhesive further comprises at least one of microspheres, and a blowing agent.

14. A reinforcing sheet, comprising: at least one layer of a reinforcing material; and a thermosetting adhesive associated with at least a portion of the reinforcing material, wherein the thermosetting adhesive includes a curing agent, and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network, wherein the curing agent is represented by at least one of the following tautomeric chemical structures: ##STR00023##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Certain embodiments of the present invention are illustrated by the accompanying figures. It will be understood that the figures are not necessarily to scale and that details not necessary for an understanding of the invention or that render other details difficult to perceive may be omitted. It will be further understood that the invention is not necessarily limited to the particular embodiments illustrated herein.

(2) The invention will now be described with reference to the drawings wherein:

(3) FIG. 1 of the drawings is a .sup.1H-NMR spectrogram of a first tautomer of a curing agent;

(4) FIG. 2 of the drawings is a .sup.13C-NMR spectrogram of a first tautomer of a curing agent;

(5) FIG. 3 of the drawings is a .sup.1H-NMR spectrogram of a second tautomer of a curing agent;

(6) FIG. 4 of the drawings is a .sup.13C-NMR spectrogram of a second tautomer of a curing agent;

(7) FIG. 5 of the drawings is a .sup.1H-NMR spectrogram of a curing agent;

(8) FIG. 6 of the drawings is a .sup.13C-NMR spectrogram of a curing agent;

(9) FIG. 7 of the drawings is a .sup.1H-NMR spectrogram of an epoxy-modified dimerized fatty acid curing agent;

(10) FIG. 8 of the drawings is a .sup.13C-NMR spectrogram of an epoxy-modified dimerized fatty acid curing agent;

(11) FIG. 9 of the drawings is a .sup.1H-NMR spectrogram of an A.sub.1 moiety;

(12) FIG. 10 of the drawings is a .sup.13C-NMR spectrogram of an A.sub.1 moiety;

(13) FIG. 11 of the drawings is an experiment in accordance with the present invention;

(14) FIG. 12 of the drawings is an experiment in accordance with the present invention;

(15) FIG. 13 of the drawings is an experiment in accordance with the present invention; and

(16) FIG. 14 of the drawings is an experiment in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(17) While this invention is susceptible of embodiment in many different forms, there is shown in the drawings and/or described herein in detail several specific embodiments with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the embodiments illustrated.

(18) In accordance with the present invention, surprisingly effective epoxy fiberglass reinforcing patches or sheets that utilize epoxy-modified dimerized fatty acids combined with an epoxy terminated polyurethane interpenetrating network (IPN) are provided herein. The patches of the present invention are suitable for use in both expandable and non-expandable heat curable applications—just to name a few.

(19) The present invention is directed to a reinforcing sheet or patch that includes: (a) one or more layers of a reinforcing material (e.g., woven fabric, woven fiberglass, etcetera) that preferably ranges in thickness from approximately 0.25 mm to approximately 5.00 mm, and more preferably ranges in thickness from approximately 0.75 mm to approximately 1.50 mm; and (b) a thermosetting adhesive associated (e.g., impregnated, etch coated, dip coated, spin coated, brush coated and/or spray coated) with at least a portion of the reinforcing material. Preferably, the thermosetting adhesive includes a curing agent (e.g., aliphatic curing agents, cycloaliphatic curing agents, polyamide curing agents, amidoamine curing agents, waterborne polyamides, latent curatives, tertiary amines, boron trifluoride-amine complexes, hydrazides, organic-acid hydrazides, dicyandiamide, etcetera), and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network.

(20) In a preferred embodiment of the present invention, the curing agent is represented by at least one of the following tautomeric chemical structures:

(21) ##STR00008##

(22) In this embodiment the first tautomer of the curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 1 and/or the .sup.13C-NMR spectrogram of FIG. 2, and the second tautomer of the curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 3 and/or the .sup.13C-NMR spectrogram of FIG. 4.

(23) In another preferred embodiment of the present invention, the curing agent is represented by the following chemical structure:

(24) ##STR00009##

(25) In this embodiment the curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 5 and/or the .sup.13C-NMR spectrogram of FIG. 6.

(26) The above-identified curing agents and/or their precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Mo.

(27) Suitable examples of epoxy-modified dimerized fatty acids include those represented by the following chemical structure:

(28) ##STR00010##

(29) wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 40 carbon atoms. In one embodiment, R.sub.1 is tall oil based.

(30) In another preferred embodiment of the present invention, the epoxy-modified dimerized fatty acid is represented by the following chemical structure:

(31) ##STR00011##
wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 35 to approximately 40 carbon atoms.

(32) In yet another preferred embodiment of the present invention, the epoxy-modified dimerized fatty acid is represented by the following chemical structure:

(33) ##STR00012##
wherein R.sub.1 is tall oil based (e.g., C36, C.sub.36H.sub.72, etcetera).

(34) In this embodiment the epoxy-modified dimerized fatty acid curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 7 and/or the .sup.13C-NMR spectrogram of FIG. 8.

(35) The above-identified epoxy-modified dimerized fatty acid and/or its precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Mo.

(36) In accordance with the present invention, suitable examples of epoxy terminated polyurethane interpenetrating networks include those represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2
wherein A.sub.1 is represented by the following chemical structure:

(37) ##STR00013##
wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 75 carbon atoms, an oligomer, and/or a polymer; and wherein A.sub.2=A.sub.1 and/or comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 35 carbon atoms, an oligomer, and/or a polymer.

(38) In a preferred embodiment of the present invention, the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2
wherein A.sub.1 is represented by the following chemical structure:

(39) ##STR00014##
wherein R.sub.1 comprises an alkyl, alkenyl, and/or alkynyl group containing approximately 1 to approximately 36 carbon atoms, an oligomer, and/or a urethane polymer; and wherein A.sub.2=A.sub.1.

(40) In this embodiment A.sub.1 generally comprises the .sup.1H-NMR spectrogram of FIG. 9 and/or the .sup.13C-NMR spectrogram of FIG. 10.

(41) The above-identified epoxy terminated polyurethane interpenetrating network and/or its precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Mo.

(42) Additional interpenetrating polymer networks are also contemplated for use in accordance with the present invention, including, for example, those disclosed in U.S. Pat. No. 4,766,183 entitled “Thermosetting Composition for an Interpenetrating Polymer Network System,” U.S. Pat. No. 4,842,938 entitled “Metal Reinforcing Patch and Method for Reinforcing Metal,” U.S. Pat. No. 5,767,187 entitled “Interpenetrating Polymer Network Compositions,” U.S. Pat. No. 6,166,127 entitled “Interpenetrating Networks of Polymers,” U.S. Pat. No. 7,429,220 entitled “Golf Balls Containing Interpenetrating Polymer Networks,” and U.S. Pat. No. 7,790,288 entitled “Interpenetrating Polymer Network as Coating for Metal Substrate and Method Therefor”—which are hereby incorporated herein by reference in their entirety, including all references cited therein.

(43) While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

(44) The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etcetera shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.

(45) The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

(46) In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

(47) As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etcetera. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etcetera. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

(48) All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

(49) Other embodiments are set forth in the following claims.